EP0646612A1 - Procédé de préparation de polyesters thermoplastiques - Google Patents
Procédé de préparation de polyesters thermoplastiques Download PDFInfo
- Publication number
- EP0646612A1 EP0646612A1 EP94115098A EP94115098A EP0646612A1 EP 0646612 A1 EP0646612 A1 EP 0646612A1 EP 94115098 A EP94115098 A EP 94115098A EP 94115098 A EP94115098 A EP 94115098A EP 0646612 A1 EP0646612 A1 EP 0646612A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkali metal
- acid
- metal compound
- alkaline earth
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 19
- 229920000728 polyester Polymers 0.000 title claims abstract description 19
- 229920001169 thermoplastic Polymers 0.000 title claims abstract description 5
- 239000004416 thermosoftening plastic Substances 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 13
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 9
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 8
- 238000009833 condensation Methods 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 230000005494 condensation Effects 0.000 claims abstract description 6
- 239000007790 solid phase Substances 0.000 claims abstract description 6
- 150000001991 dicarboxylic acids Chemical class 0.000 claims abstract description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 4
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 4
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- -1 aliphatic diols Chemical class 0.000 description 5
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical class CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical class CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- 229920001283 Polyalkylene terephthalate Polymers 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical class CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012170 montan wax Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical class CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- CFQZKFWQLAHGSL-FNTYJUCDSA-N (3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e,17e)-18-[(3e,5e,7e,9e,11e,13e,15e)-octadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoyl]oxyoctadeca-3,5,7,9,11,13,15,17-octaenoic acid Chemical compound OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\OC(=O)C\C=C\C=C\C=C\C=C\C=C\C=C\C=C\C=C CFQZKFWQLAHGSL-FNTYJUCDSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical class COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Chemical class 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 101100117236 Drosophila melanogaster speck gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 1
- YJLYANLCNIKXMG-UHFFFAOYSA-N N-Methyldioctylamine Chemical compound CCCCCCCCN(C)CCCCCCCC YJLYANLCNIKXMG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005228 aryl sulfonate group Chemical group 0.000 description 1
- 150000001559 benzoic acids Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical class OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- WOSVXXBNNCUXMT-UHFFFAOYSA-N cyclopentane-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1CC(C(O)=O)C(C(O)=O)C1C(O)=O WOSVXXBNNCUXMT-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Chemical class 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical class ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical class C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000004707 phenolate Chemical class 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- PRWXGRGLHYDWPS-UHFFFAOYSA-L sodium malonate Chemical compound [Na+].[Na+].[O-]C(=O)CC([O-])=O PRWXGRGLHYDWPS-UHFFFAOYSA-L 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- JXKPEJDQGNYQSM-UHFFFAOYSA-M sodium propionate Chemical compound [Na+].CCC([O-])=O JXKPEJDQGNYQSM-UHFFFAOYSA-M 0.000 description 1
- 239000004324 sodium propionate Substances 0.000 description 1
- 235000010334 sodium propionate Nutrition 0.000 description 1
- 229960003212 sodium propionate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000008117 stearic acid Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 235000019386 wax ester Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/80—Solid-state polycondensation
Definitions
- solid-phase post-condensation is often carried out in at least a second stage of the reaction.
- the present invention was therefore based on the object of making available a process for the preparation of polyesters of the type mentioned at the outset which provides a largely speck-free and gel-free product and, overall, requires a shorter polycondensation time.
- thermoplastic polyesters by multi-stage polycondensation of dihydroxy compounds with dicarboxylic acids or their esters or their ester-forming derivatives, an alkali metal compound or an alkaline earth metal compound in an amount of 1 to 10 mmol per kg of polyester, calculated as alkali metal or Alkaline earth metal added and at least one further stage is carried out as a solid phase condensation.
- polyesters with a high molecular weight and largely free of specks and gel are accessible, in particular with solid-phase condensation, with a shorter polycondensation time.
- Aliphatic, aromatic or cycloaliphatic diols can be used as dihydroxy compounds.
- Examples include ethanediol (ethylene glycol), 1,3-propanediol, 1,4-butanediol, cyclohexanediols, hydroquinone, resorcinol and bisphenol A, of which ethanediol and 1,6-butanediol are particularly preferred.
- ethanediol ethylene glycol
- 1,3-propanediol 1,4-butanediol
- cyclohexanediols hydroquinone
- resorcinol and bisphenol A of which ethanediol and 1,6-butanediol are particularly preferred.
- Aliphatic and / or aromatic dicarboxylic acids with preferably 4 to 20, in particular 4 to 12, carbon atoms can be used as dicarboxylic acids.
- Examples include isophthalic acid, phthalic acid, terephthalic acid, alkyl-substituted derivatives of the abovementioned acids, naphthalenedicarboxylic acids (2.6 and 2.7), aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid and decanedicarboxylic acid, of which iso- or terephthalic mixtures are particularly preferred become.
- the polyesters produced according to the invention can also contain relatively small amounts, advantageously less than 10 mol%, based on the respective monomer component, of further units which are derived, for example, from hydroxycarboxylic acids.
- inorganic and organic compounds of alkali metals preferably of Li, Na, K, particularly preferably Na compounds, are suitable.
- suitable inorganic compounds of the (earth) alkali metals are the corresponding silicates, phosphates, phosphites, sulfates or, preferably, carbonates, hydrogen carbonates and hydroxides.
- the organic compounds of the (earth) alkali metals include the corresponding salts of (cyclo) aliphatic, araliphatic or aromatic carboxylic acids with preferably up to 30 C atoms and preferably 1 to 4 carboxyl groups.
- salts with different types of acid residues e.g. Alkali paraffin, alkali olefin and alkali aryl sulfonates or also phenolates and alcoholates, such as e.g. Methanolates, ethanolates, glycolates
- Sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium salts of mono- and polycarboxylic acids, in particular the aliphatic mono- and polycarboxylic acids, preferably those having 2 to 18 carbon atoms, in particular having 2 to 6 carbon atoms and up to four, preferably up to two, are preferred Carboxyl groups, as well as sodium alcoholates with preferably 2 to 15, in particular 2 to 8, carbon atoms are used.
- Examples of particularly preferred representatives are sodium acetate, sodium propionate, sodium butyrate, sodium oxalate, sodium malonate, sodium succinate, sodium methoxide, sodium ethanolate, sodium glycolate.
- Sodium methoxide is very particularly preferred, which is used particularly advantageously in an amount of 2.5 to 5 mmol, calculated as Na. Mixtures of different (earth) alkali metal compounds can also be used.
- the (earth) alkali metal or the (earth) alkali metal compound are added at any point in a first stage of the synthesis of the polyester, which generally follows the
- Esterification / polycondensation process but preferably carried out according to the transesterification / polycondensation process. Addition at the beginning of the transesterification is particularly preferred when using the transesterification / polycondensation process.
- the esterification / polycondensation process and the transesterification / polycondensation process are well known and are described, for example, in Ullmann's Encyklopadie der industrial chemistry (4th ed.) 19 , pp. 61 to 88 (1980).
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4333930A DE4333930A1 (de) | 1993-10-05 | 1993-10-05 | Verfahren zur Herstellung von thermoplastischen Polyestern |
| DE4333930 | 1993-10-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0646612A1 true EP0646612A1 (fr) | 1995-04-05 |
| EP0646612B1 EP0646612B1 (fr) | 1999-04-14 |
Family
ID=6499457
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP94115098A Expired - Lifetime EP0646612B1 (fr) | 1993-10-05 | 1994-09-24 | Procédé de préparation de polyesters thermoplastiques |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5610231A (fr) |
| EP (1) | EP0646612B1 (fr) |
| DE (2) | DE4333930A1 (fr) |
| ES (1) | ES2129560T3 (fr) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4787287A (en) * | 1986-05-30 | 1988-11-29 | Rheinmetall Gmbh | Automatic cannon having an ammunition-receiving device |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1585779B1 (fr) * | 2003-01-23 | 2010-03-10 | Saudi Basic Industries Corporation (Sabic) | Complexe catalyseur destine a catalyser les reactions d'esterification et de trans-esterification et procede d'esterification / trans-esterification reposant sur l'utilisation dudit complexe |
| US8557950B2 (en) | 2005-06-16 | 2013-10-15 | Grupo Petrotemex, S.A. De C.V. | High intrinsic viscosity melt phase polyester polymers with acceptable acetaldehyde generation rates |
| US7655746B2 (en) * | 2005-09-16 | 2010-02-02 | Eastman Chemical Company | Phosphorus containing compounds for reducing acetaldehyde in polyesters polymers |
| US9267007B2 (en) * | 2005-09-16 | 2016-02-23 | Grupo Petrotemex, S.A. De C.V. | Method for addition of additives into a polymer melt |
| US7838596B2 (en) * | 2005-09-16 | 2010-11-23 | Eastman Chemical Company | Late addition to effect compositional modifications in condensation polymers |
| US7932345B2 (en) | 2005-09-16 | 2011-04-26 | Grupo Petrotemex, S.A. De C.V. | Aluminum containing polyester polymers having low acetaldehyde generation rates |
| US8431202B2 (en) | 2005-09-16 | 2013-04-30 | Grupo Petrotemex, S.A. De C.V. | Aluminum/alkaline or alkali/titanium containing polyesters having improved reheat, color and clarity |
| US7709595B2 (en) * | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum solutions made with polyhydroxyl ether solvents |
| US20080027207A1 (en) * | 2006-07-28 | 2008-01-31 | Jason Christopher Jenkins | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with mono-ol ether solvents |
| US7745368B2 (en) * | 2006-07-28 | 2010-06-29 | Eastman Chemical Company | Non-precipitating alkali/alkaline earth metal and aluminum compositions made with organic hydroxyacids |
| US7709593B2 (en) * | 2006-07-28 | 2010-05-04 | Eastman Chemical Company | Multiple feeds of catalyst metals to a polyester production process |
| US8901272B2 (en) * | 2007-02-02 | 2014-12-02 | Grupo Petrotemex, S.A. De C.V. | Polyester polymers with low acetaldehyde generation rates and high vinyl ends concentration |
| ES2617527T3 (es) * | 2013-03-18 | 2017-06-19 | Basf Se | Poliéster para extrusión de perfiles y/o extrusión de tubos |
| WO2020226200A1 (fr) * | 2019-05-07 | 2020-11-12 | Tlc Korea Co., Ltd. | Résine de copolyester biodégradable produite par estérification et polycondensation d'acide dicarboxylique aliphatique dérivé de biomasse et d'acide dicarboxylique aromatique avec un diol et procédé de production associé |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT290132B (de) * | 1968-03-28 | 1971-05-25 | Alpine Chemische Ag | Verfahren zur Herstellung von Polyestern und Copolyestern |
| EP0215364A2 (fr) * | 1985-09-09 | 1987-03-25 | Hoechst Aktiengesellschaft | Procédé pour la préparation de compositions de polyester à cristallisation rapide |
| US4654413A (en) * | 1984-12-28 | 1987-03-31 | Polyplastics Co., Ltd. | Manufacturing of high molecular weight polyester |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2507776C2 (de) * | 1975-02-22 | 1983-09-22 | Bayer Ag, 5090 Leverkusen | Schnellkristallisierende Poly(äthylen/alkylen)-terephthalate |
| DE3067764D1 (en) * | 1979-09-21 | 1984-06-14 | Ici Plc | Fast crystallising block copolyester composition |
| DE3532033A1 (de) * | 1985-09-09 | 1987-03-19 | Hoechst Ag | Schnellkristallisierende polyestermassen und verfahren zu deren herstellung |
| JPS6454026A (en) * | 1987-08-24 | 1989-03-01 | Dai Ichi Kogyo Seiyaku Co Ltd | Production of modified polyester |
-
1993
- 1993-10-05 DE DE4333930A patent/DE4333930A1/de not_active Withdrawn
-
1994
- 1994-09-24 EP EP94115098A patent/EP0646612B1/fr not_active Expired - Lifetime
- 1994-09-24 ES ES94115098T patent/ES2129560T3/es not_active Expired - Lifetime
- 1994-09-24 DE DE59408109T patent/DE59408109D1/de not_active Expired - Lifetime
-
1996
- 1996-04-17 US US08/633,521 patent/US5610231A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT290132B (de) * | 1968-03-28 | 1971-05-25 | Alpine Chemische Ag | Verfahren zur Herstellung von Polyestern und Copolyestern |
| US4654413A (en) * | 1984-12-28 | 1987-03-31 | Polyplastics Co., Ltd. | Manufacturing of high molecular weight polyester |
| EP0215364A2 (fr) * | 1985-09-09 | 1987-03-25 | Hoechst Aktiengesellschaft | Procédé pour la préparation de compositions de polyester à cristallisation rapide |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4787287A (en) * | 1986-05-30 | 1988-11-29 | Rheinmetall Gmbh | Automatic cannon having an ammunition-receiving device |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4333930A1 (de) | 1995-04-06 |
| US5610231A (en) | 1997-03-11 |
| DE59408109D1 (de) | 1999-05-20 |
| ES2129560T3 (es) | 1999-06-16 |
| EP0646612B1 (fr) | 1999-04-14 |
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